Wood stain and filling composition



Unite WOOD STAIN AND FILLING COMPOSITION No Drawing. Application April 13, 1955, Serial No. 501,170

2 Claims. (Cl. MiG-34) This invention relates to stains, especially combination stains and fillers for use on wood and to compositions for use in staining and filling Wood surfaces and the like, as well as methods for staining such articles.

The art of wood staining in the past has made use of dyes which were dissolved or dispersed in solvents and the like diluents so as to make the same applicable for applying as a spray, dip, or by brush. The water soluble stains generally consisted of an aqueous solution of an aniline dye, and were applied by brushingthe same on to the wood surface to be stained. Such water stains, however, exhibit the very undesirable effect of raising the grain of the wood. This raising of the grain necessitates that theusrface be sanded or otherwise treated to render it smooth. The grain raising effect of such water soluble stains also makes it necessary to apply a sealer coating such as shellac to the stained wood in order to stiffen the fibers of the wood so that the surface can be uniformly sanded. When an open grain wood is used, it is'necessary after the sanding operation to apply a filler to the surface over which is then applied a varnish, lacquer or other desired coating.

The non-aqueous stains, for example, oil stains and spirit stains, and which generally consist of an aniline dye or aniline dye base dissolved in an organic solvent such as a hydrocarbon or alcohol, have been extensively used and have certain advantages over water stains. They also have certain undesirable features. The use of hydrocarbons, such as benzol, toluol or other petroleum distillates that are highly volatile when applied to thesurface to be treated tends to leave the pores of the wood unimpregnated with the dye. They are'also dangerous in mass application in a furniture factory. Where such composition is applied to a wood surface having open grain, it has been the practice after drying to treat the surface with a filler. Again, before applying the finish coating of varnish or lacquer, there must be applied a coating of shellac or similar functioning coating over the stain or the filler in order to prevent bleeding. This application of shellac or the like is necessary, otherwise the solvents of the varnish or lacquer will penetrate into the stain and cause the color to bleed into the finished coat. The use of hydrocarbon solvents also is undesirable from the standpoint of fire hazard and the effect the volatile solvent may have on the operator applying the stain.

The spirit stains are not as useful as the water stains because they are subject to the disadvantage that such stains do not penetrate into the wood'stains and they further lack permanency of color and 'tend to fade in use, similar as the oil type stains. Spirit stains are also subject to the bleeding effect, and inmany instances, also produce the undesirable grain raising upon application to the Wood surface.

In accordance with the present invention, I have discovered that by combining the citrus fiavanone derivatives,

for example, hesperetin, naringenin and. eriodictyol found in citrus pulp and citrus waste, with aniline o'r' aniline bases, and dispersing the resultant dye in'water solution Patenti ICE that this new combination provides an excellent wood stain and filler composition with unexpected results. This citrus-aniline dye compound can be readily fixed in the cellulose pores of the wood as it is derived from cellulose and is compatible with it.

It may be-applied as a hot or cold solution to the wood. A hot aqueous solution of such citrus-azo dyes as derived from these citrus fiavanone glucosides obtained from citrus wastes, being derived from a cellulose source, forms a stain which is completely compatible with the wood so that a highly desirable stain effect is produced with complete dispersion of uniform character and deep penetration.

The aqueous staining solutions of this invention which comprise the aforementioned citrus-azo dye are preferably applied as a hot aqueous solution, although it is also effective as a wood stain when applied as a cold solution. Hot aqueous solutions of such dyes when applied penetrate into the wood and the solvent evaporates before the grain ofthe wood is caused to raise. Upon cooling, the dye is set in the wood and forms a smooth uniformly stained wood surface which requires no sanding or other treatment to produce a desirable surface upon which a finish coatingof varnish or lacquer may be applied.

In thismanner, the invention provides a wood staining composition which is very inexpensive and easy to manufacture, and wherein the use of expensive organic dilucuts and solvents and the like, with their attendantdisadvantages may be entirely eliminated.

A typical formula of eriodictyol is as follows:

In accordance with the present invention, I have found that dyestuffs 'such as obtained by coupling a diazotized aromatic amino compound, preferably one containing at least one substituted benzene nucleus or a naphthalene nucleus, with a flavanone, e. g. maringenin, hesperetin .and eriodictyol, derived from citrus waste products, are

useful for staining woods. Employing these flavanones, which are also referred to as glucosides, as a coupling component provides what may be called a citrus-azo dye.

These citrus-azo dyes are soluble in water and in methanol to a limited degree, being very slightly soluble in Carbitol and Cellosolve. They are insoluble in hydrocarbons, esters and higher alcohols. Higher temperatures do not appreciably increase solubility in these solvents.

In the use of such dyes, an advantage lies in the fact that they are insoluble in the customary solvents audit is possible to provide a rapidly volatizing organic solvent 3 vehicle or carrier in which the dye is substantially insoluble.

A further advantage is derived in that, once applied, such wood stains are not subject to injury by the solvent action of hydrocarbons, esters, alcohols, etc. An aqueous solution of the dye, therefore, maintains its original good staining properties despite the association with rapidly volatizing organic solvents or when used with carriers, such as glycols, others, alcohols and the benzene series of hydrocarbons.

These dyes stained the wool well, with good clarity and non-bleeding into succeeding coats. The darker dyes are more soluble than the red dyes. The darker dyes can be made in as high as a ten ounce solution as contrasted with the usual two ounce solution in the lighter dyes.

Illustrative of the method of producing the azo dyes for use in preparing aqueous wood stains is as follows:

Example I (1) To a slurry comprising 0.1 mole of aniline in water is added 0.25 mol of hydrochloric acid. The mixture is diluted with water and cooled to a temperature of between about 15 C. While maintaining the temperature of the mixture at about 10 C., there is added slowly over a period of about 10 to 15 minutes a 0.1 mol sodium nitrite. The mixture is stirred slowly while maintaining the temperature at about 10 C. for one-half an hour.

(2) To effect the coupling reaction a slurry comprising 0.1 mol of resperetin in an aqueous solution containing 0.3 mol of sodium hydroxide is employed. The mixture is diluted with water and cooled to between 5 and C. Thereafter, the diazo of (1) is stirred into the mixture over a minute period while maintaining the temperature at about 1015 C. and the pH of the solution above 9. After stirring the mixture for half an hour more the dyestufi is isolated by adjusting the pH of the solution to neutral with dilute hydrochloric and adding a salt, i. e., sodium chloride or sodium sulfate, until the dye precipitates from the solution. Thereafter, the mixture is filtered to recover the dyestufi.

Example 11 A combination stain and filler composition made utilizing the citrus azo dye of Example I is as follows:

Parts by weigh Citrus azo dyestuff (Exp. 1) Fine silica (300 mesh) 8-10 Methanol 1-2 Water l-2 In compounding the above wood stain and filler, the dye may be stirred into the water and methanol mixture followed by addition of the filler.

As a solvent and filler variation, the following is given as illustrative:

Example III 'Water 1-2 The composition is compounded as described in EX- ample II. In place of wood flour or a portion thereof corn starch may be substituted therefor as desired.

Example IV To provide a wood stain and filler having good penetrating properties and yet non-grain raising, the following is exemplary:

Parts by weight Citrus azo dyestufli (Exp. I) 1-3 Silex (fine silica) 5-10 Methanol 2-3 Toluol 1-2 Diethylene glycol monoethyl ether 1-2 Water 1-2 The glycol ether provides increased penetration qualities and improves the non-grain raising properties of the stain. In place of a part or all of the monoethyl ether compound, the mono-methyl ethyl ether derivative may be used.

Example V In this example, aniline is diazotized in the usual manner and coupled with maringenin (or a mixture of naringenin and hesperetin) as the glucoside or flavanone coupling substance.

Example VI Variations of naringenin azo dyestuffs are made by carrying out the coupling as described in Example I employing other amines or amino compounds in place of aniline, such as l-naphthamine 4 sulphonic acid, 2 amino 8 naphthol sulfonic acid and p-nitroaniline.

Example VII Similarly variations of hesperetin azo dyestuffs are prepared by effecting a coupling action as described in Example I utilizing instead of aniline, other amino compounds such as l-naphthalene 4-sulfonic acid, 2-amino 8 naphthol 6 sulfonic acid and 5 nitro 2 aminazo.

Example VIII A combination stain and filler composition is prepared as in Example II except that the citrus azo dyestufi used is as described in Example V and which produces a difierent hue or shade of color.

Example IX In this compisition Example III is repeated using a modified citrus azo dyestutr' as described in Example VI.

Example X In this instance a wood stain and filler composition is prepared as described in Example IV and substituting the hesperetin coupled azo dyestuff of Example VII for that of Example I.

The invention broadly includes the preparation and use of wood staining compositions comprising as a principle staining constituent a water-soluble azo dyestutf containing the grouping in which A represents the residue of an aromatic amino compound, N is nitrogen and B is a glucoside or flavanone coupling such as found in citrus wastes, as aforementioned.

Varied shades of color may be produced with the citrus azo dyestufls, depending on the particular amine and glucoside or fiavanone used in compounding the dyestuff.

The amount of dye utilized in a given case depends upon the particular dye employed and its degree of concentration, and, of course, the depth of color required for the particular stain.

Additional solvent and vehicle ingredients may be added to the chosen citrusazo dye (as described in the patent to Bush No. 2,000,121 of May 7, 1935) to secure the particular properties desired in the final composition. In choosing such additional solvents or diluents or other vehicles, several factors should be kept in mind. The solvents or diluents or additional vehicles utilized should preferably be inexpensive enough to make them commercially practicable for the use in hand. They ,should be solvents of or miscible with the dye dissolved in the penetrant vehicle component, and should be of such nature as to penetrate the wood and carry the dye into the wood. Further, the composition should desirably include a water eliminant in order to give the composition properties of resistance to moisture retention. Further, the combination of solvents or diluents or vehicles should be such that the final composition exhibits a proper evaporation curve to dispel both the diethyleneglycol mono-ethyl ether or other penetrant vehicle and any moisture present from the wood surface.

As illustrative of ingredients that may be utilized in order to increase the rapidity of drying and setting of the composition, the aliphatic alcohols, such as methyl alcohol, ketones, such as acetone, and the esters of the aliphatic alcohols, particularly the fatty acid esters of such materials, namely, ethyl acetate, etc. may be utilized. Methyl alcohol or methanol is a particularly valuable ingredient for use in this connection.

Ingredients that give the composition resistance to moisture retention include hydrocarbon distillates, particularly the coal tar distillates, benzol, toluol, solvent naphtha, the xylols, ethyl benzene, etc. Toluol is particularly valuable in this connection. Many of the esters, such as butyl propionate and butyl acetate are also exemplary of materials which have water elimination properties, but such materials as these esters are slower drying and cost more, and, therefore, are not as valuable in general in compositions of the present character as are the hydrocarbon substances, such as toluol. Both the aliphatic alcohols and similar ingredients and the hydrocarbon distillates and similar ingredients aid in the penetration and evaporation and other desirable efiects above mentioned.

While for the production of stain and filler compositions, particularly for treating wood surfaces, the compositions hereinabove described may be utilized, other additional ingredients may be added to the composition or mixtures thereof for particular purposes. For instance, other fillers and pigments may be substituted for those hereinbefore mentioned in compounding wood stain and filler compositions. For example, powdered chalk, carbon black, lamp black and oil paste fillers or mixtures thereof may be used to produce the desired shade or color staining effect.

In addition, the citrus azo dye stains produced in accordance with this invention, or the stain bases, may be added to or incorporated with cellulose ester or ether solutions and lacquers, as well as other lacquers, par

ticularly those containing solvents of the nature of alcohols and hydrocarbons. In this way, color dipping lacquers, the color of which is fast, may be produced. Various types of nitrocellulose compositions may, for

example, be combined with the stain bases or compositions of the present invention.

In accordance with the present invention, it is possible for the first time to utilize such water soluble azo dyes made by coupling a flavanone derivative, such as naringenin, eriodictyol or hesperetin with aniline or other suitable diazotizing amino compound to form a water soluble dye which yields, upon dispersion in an aqueous vehicle, a wood stain which is substantially fast to light, and exhibits non-fading, non-grain raising properties. A wood stain also is provided, which when properly compounded and applied as described, does not bleed through lacquer or varnish top finishing coats. Thus, the use of intermediate sealing coats is not necessary. Where desired, of course, intermediate sealing coats of suitable type may be employed.

This application is related to the application, Serial No. 277,920, filed March 21, 1952, now abandoned.

It will be understood that while there have been described herein certain specific embodiments of this invention, it is not intended thereby to have it limited to or circumscribed by the specific details given in view of the fact that this invention is susceptible to various modifications and changes which come within the spirit of this disclosure and the scope of the appended claims.

I claim:

1. A combination wood stain and filling composition which is non-grain raising and consisting essentially of the following constituents in parts by weight 1 to 3 parts of an azo dye in which the coupling component is chosen from the group consisting of naringenin, hesperetin and eriodictyol, 5 to 10 parts of finely divided silica, 2 to 3 parts of methanol, 1 to 2 parts of toluol, l to 2 parts of water, and 1 to 2 parts of a glycol ether selected from the group consisting of diethylene glycol mono-ethyl ether and diethylene glycol mono-methyl ether.

2. A combination wood stain and filling composition which is non-grain raising and consisting essentially of the following constituents in parts by weight 1 to 3 parts of an azo dye in which the coupling component is chosen from the group consisting of naringenin, hesperetin and eriodictyol, 5 to 10 parts of finely divided silica, 2 to 3 parts of methanol, 1 to 2 parts of toluol, .l to 2 parts of water, and 1 to 2 parts of diethylene glycol n1onoethyl ether.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A COMBINATION WOOD STAIN AND FILLING COMPOSITION WHICH IS NON-GRAIN RAISING AND CONSISTING ESSENTIALLY OF THE FOLLOWING CONSTITUENTS IN PARTS BY WEIGHT 1 TO 3 PARTS OF AN AZO DYE IN WHICH THE COUPLING COMPONENT IS CHOSEN FORM THE GROUP CONSISTING OF NARINGENIN, HESPERETIN AND ERIODUCTYOL, 5 TO 10 PARTS OF FINELY DIVIDED SILICA, 2 TO 3 PARTS OF METHANOL, 1 TO 2 PARTS OF TOLUOL 1 TO 2 PARTS OF WATER, AND 1 TO 2 PARTS OF A GLYCOL ETHER SELECTED FROM THE GROUP CONSISTING OF DIETHYLENE GLYCOL MONO-ETHYL AND DIETHYLENE GLYCOL MONO-METHYL ETHER. 